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UNITED ST BUIBERT ARNOT, OF ZUELCH. SWITZERLAND.

AZO DYE AND ITS PR-DCESE F NLANUFACTURE.

No Drawing.

T 0 all whom it may concern Be it known that I. Dr. Rom-3m Rumor. chemist, a citizen of the Republir oi Czecho-Slovakia. residing at Zurirln Ssh zerland, have invented certain new and useful Improvements in or Relating to .x no Dyes and their Processes of Manul'arture. (for which I have filed applications in Hermany Ma 7, 1917, in England July 522. 1920, and in France.) of which the following is a specification.

On the subject of nitroderivatives of re tene and its del ivatires there is hardly any thing to be found in literature, although nitro products are easily obtainable. If retene, retenequinone or retene sulto-zuzid is subjected to the action of fuming nitric acid, the nitro products from the first two gin quickly into solution in the cold state with a red-brown 00h) and se iarate out on the addition of water, as yellow flakes. while the intro-substance of the sull'o-a rid remains in solution. The nitro-suhstanees oi reteue and retenequinone have the peruliarily ot beinp rather diiiicult to tll SlllYP in alkalis; it it is desired therefore to obtain the amine: in alkaline solution, it is advisable to d solve the nitro substances in alroholized al kali. The diazonium combinations combine readily and in large quantity with lhe usual reagents. For the production oi nitro-retene it is not necessary to PlUkllHt the l'etene in a. pure state; it is sullirient to tr mt with fuming nitric arid the part, so i'alled tar tallow distilling over in vat-mun in the preparation of the resinous oil from pine tar at 250- 380, and whirh ronsists mainly of retene (Ekestranrl. Lv'whi r a .lNll. 1%. page 75).

In concentrated cold nitrie EH i-l reti-ne is insoluble. )n being heated i4: i lRrolufi foaming and bubhling. with a yeilou rolor. The addition of waler muses the nilro sol stance to preripilate as a yellow o posil. Nitratin e is more easily cilia-ted with tune in; nitrir acid. wlu-rei ore the latter is prei erable as a nitration" mediumv Example 1.

One part retene is added to i parts fuming nitrie arid stirring the while at a temperature of 15. and thereafter gradually heated in a water bath for 1 hour to a tenuueratuie of 90 The red brown sohuion is leit standinp for 12 hours and then enipliwh while stirring; into cold water, whereupon a Specification of Letters P tent.

Application filed. fictober 12, 1.926.

Patented Uri. 25, 1921.

Serial No. 416.517.

lennziryellow flak precipitate makes iLs appr amnre'Whirl) drained ott. repeatedly as d and dried. It is only with diiiirulty solul le in soda-solution. ammonia. eon rentratec'l solution of sodium hydroxid or ligroin; but on the other hand it is easily soluble in aieoholie ailtalhether. warm methyl and ethyl alcohol. rhloroforin. glaeial acetic arid or benzol. Four parts nitrated relene are dissolved in 25 parts c nu'einrated Hit")- holir solution of caustic soda; 75 parts water and lzi parts sodium hydrosultite (80%) are added and the mixture boiled for two hours; after which concentrated llYKllOL'lllOl'lO acid is added till acid reartion sets in and the suirurous acid is expelled by vigorous boil Eng brown body now separates out whirl: is tiltrated oil; in the filtrate is to be l'onnd ihe hydrorhlorie reteneamiu whieh, after cooling with ice is diazolized with 6 pails of a lUji, s lution of sodium nitrite. The diaxoniuln rompound forms with R salt violet. with (i salt browlrred. with Andersen's salt red. with H aeid violet, with alpha naphthol red. The diazoniuni romhination is. while heizr; stirred. allowed to pass into a solution of El parts ill-salt and 1 part ('ah-ined soda, in 40 parts water, the mixture is again stirred for an hour, the red-violet solution of coloring material is heated to hoiliup point and finely powdered roimuon salt is added till precipitation sets in. \iler vooling the dye stuli' is thereupon rapidl drained oil and dried on clay. In an arid hath it dyes wool and silk in a bluishred tint and the dyeing bath is not discolored. The wo l is pla .(l in the bath at a tempera ture of SW and very gradually 2'}? of sul l'oiharid is added, the wool then being left in ihe hath for one hour at :1 temperature fil cooling it becomes given again, and it holilYtH in the sann- Way as rctenequinons to- Mrzd hot and mid alcolui/iir solutions oi caustitallzalis, a Fact to which E. Banil' r already drier. attontion in the .i mml page 119. A red coloration takes place when alkali added to a warm alcohoiic solution of nit .li'ed rctvnsqninono and on cooling tho decoloration sets in again. To obtain the amin 4 parts nitroi'elonu quinone are dissolvcd 'n :n parts cou-en tinted alcoinilic alkali and Emili for two hours on the rctlu .'(in1nlen tr with 3'" guirts water and 12 ports; oi Fau solution of sodium hydrosulfite. vsiu-areaiter it is acidnlat-ed withhydrochloric acid and the solfurous acid is removal h boiling and then filtered. The amin will he found in the filtrate and after living cooled with ice. is diazotizsd with 5.5 part" of :1 10}; :-r.;]ution of nitrite. The iliazmiium solution forms with R-salt a Winl.- (i, with (isalt a brownred. with Ander cns salt a fuchsiared, with H -aei l violet. with beta naphihol W1nered, with alpha napldh laliuin a dark violet. The diazonium solution is poured while stirring into a olution of two parts Rsalt and one part caliined soda. in 35 parts miter and tho ageing material further worked up exactly in Example 1. The Iinal dyeing;- takes place in similar fashion, when a bluish-rod tint is obtained.

hour parts of retene arc added to 20 parts of fuming sulfuric acid (20% 80 the. whole being ice-cooled and then gradually raised to a temperature, of 90 for an hour. Into the mixture when Well cooled is p ured 12 parts concmitralwl nitric acid, with agitation and the nitro proluct after heinp tiilUWttl to stand f r hours. is poured on ice, \il?.?l8 tluviscous brown substance goes into solution with a yellon color. To this solution is :uldcd an excess ot iron in the form of powder. then boiled for two hours. The iron is pruzipitatcd by allialis. filtered off and after acidification, 9 parts of a 10% solution of sodium nitrite are poured into the well cooled filtrate. The diazotized retene sulEo-acid couples with B salt red-brown, with G-salt brown, with Andcrscns salt red, with H-acid purplered. The diazoniumsolution is stirred into a solution consistin of 4% parts R-salt, and li its calcined sot a in parts water; the red-hrown dyeing material is left standing during 1 hour and then dried by evaporation. The dyeing material left behind is then reduced to a owder. The dyeing is carried out as in txamplo 2, when a redhrown tint is obtained.

Since certain derivatives, homoiogues and substitution products of retene will act similarly to retene. it is to be understood that such compounds are included by the term retene as used in the claims.

I claim- 1. The diazonium compounds of rote-no which form with R salt reddish to violet dyes, with G salt brown to brown-rod dyes, with Anilersons salt reddish dyes, and with H acid violet to purple red dyes.

2. A. (lye compound having a diazonium compound of rctono radical in its molecule.

3. Ann-dyestuffs comprising diazdcom binations of retens coupled with azo dyestufl' components.

4. A process for making azo-dyestufls comprising coupling (limo-combinations of rotene with azo-dyestuff components.

5. A process of making an intermediate compound for making dyes, which comprises nitrating retort-e, reducing the resulting nitro compound to amin and diazotizing said amin.

In testimony whoreol. I have hereunto set my hand in pres nce of two subscribing Witncsses.

Du. ROBERT ARNOT.

"itnesses U. M. Dnmo. A noUsT Rondo. 

